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Structure and electronic properties of rare earth DOBDC metal–organic-frameworks

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C9CP04038B· OSTI ID:1574447
 [1];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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In our report, we apply density functional theory (DFT) to investigate rare-earth metal organic frameworks (RE-MOFs), RE12(μ3-OH)16(C8O6H4)8(C8O6H5)4 (RE = Y, Eu, Tb, Yb), and characterize the level of theory needed to accurately predict structural and electronic properties in MOF materials with 4f-electrons. A two-step calculation approach of geometry optimization with spin-restricted DFT and large core potential (LCPs), and detailed electronic structures with spin-unrestricted DFT with a full valence potential + Hubbard U correction is investigated. Spin-restricted DFT with LCPs resulted in good agreement between experimental lattice parameters and optimized geometries, while a full valence potential is necessary for accurate representation of the electronic structure. The electronic structure of Eu-DOBDC MOF suggested a strong dependence on the treatment of highly localized 4f-electrons and spin polarization, as well as variation within a range of Hubbard corrections (U = 1–9 eV). For Hubbard corrected spin-unrestricted calculations, a U value of 1–4 eV maintains the non-metallic character of the band gap with slight deviations in f-orbital energetics. When compared with experimentally reported results, the importance of the full valence calculation and the Hubbard correction in correctly predicting the electronic structure is highlighted.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; SC0012577; NA0003525
OSTI ID:
1574447
Alternate ID(s):
OSTI ID: 1570052
Report Number(s):
SAND--2019-12496J; 680399
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 41 Vol. 21; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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